3d printing system comprising solid build ink comprising colorant

ABSTRACT

A color three-dimensional (3D) printing system includes (1) a solid build ink for each of a plurality of colors, each solid build ink includes (a) a solid acrylate in an amount from about 40 to about 70 percent by weight, (b) a non-curable wax in an amount from about 10 to about 45 percent by weight, (c) a curable wax in an amount from about 1 to about 15 percent by weight, (d) a photoinitiator, and (e) a colorant; each solid build ink has a curing speed adjusted by a ratio of the non-curable wax to curable wax such that the initial curing speed and final hardness of each solid build ink is approximately the same for each of the plurality of colors, and (2) a support material includes the non-curable wax used in each build ink, the support material providing a scaffold for deposition of each build ink.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of co-pending U.S. patentapplication Ser. No. 14/630,629, filed Feb. 24, 2015, which is hereinincorporated by reference in its entirety.

BACKGROUND

The present disclosure relates to three-dimensional printing. Inparticular, the present disclosure relates to three-dimensional printingemploying UV curable solid inks capable of carrying diverse colorants.

Three-dimensional (3D) printers are becoming increasingly popular inhome and professional applications. There are many advantages to using3D printers, including quicker, more economical and high throughputprototype evaluation. 3D printers currently offer a number of solutionsfor selective deposition modeling for professional use.

A typical printing system applies a UV curable hot melt material to anon-curable wax support via inkjet. Each layer, typically microns insize, is cured after deposition. When the fabrication is complete, thesupport material is washed, melted or blasted away, depending on itscomposition, leaving the 3D fabrication. The UV curable materials areavailable in a wide variety of physical characteristics (e.g., tensilestrength, tensile modulus, flexural strength, and the like), but in alimited number of colors, and using different colors presents aparticular challenge due to differing rates of curing and final curinghardness value which may preclude printing articles with multiplecolors.

SUMMARY

In some aspects, embodiments herein provide color three-dimensional (3D)printing systems comprising (1) a solid build ink for each of aplurality of colors, each solid build ink comprising (a) a solidacrylate in an amount from about 40 to about 70 percent by weight, (b) anon-curable wax in an amount from about 10 to about 45 percent byweight, (c) a curable wax in an amount from about 1 to about 15 percentby weight, (d) a photoinitiator, and (e) a colorant, wherein each solidbuild ink has a curing speed adjusted by a ratio of the non-curable waxto curable wax such that the initial curing speed and final hardness ofeach solid build ink is approximately the same for each of the pluralityof colors, and (2) a support material comprising the non-curable waxused in each build ink, the support material providing a scaffold fordeposition of each build ink.

In some aspects, embodiments herein provide methods of color 3D printinga three-dimensional article comprising (1) providing a solid build inkfor each of a plurality of colors, each solid build ink comprising (a) asolid acrylate in an amount from about 40 to about 70 percent by weight,(b) a non-curable wax in an amount from about 10 to about 45 percent byweight, (c) a curable wax in an amount from about 1 to about 15 percentby weight, (d) a photoinitiator, and (e) a colorant, wherein each solidbuild ink has a curing speed adjusted by a ratio of the non-curable waxto curable wax such that the curing speed and final hardness of eachsolid build ink is approximately the same for each of the plurality ofcolors, (2) providing a support material comprising the non-curable waxused in each build ink, the support material providing one or morescaffold layers for deposition of at least one solid build ink layer asdictated by the geometry of the three-dimensional article, (3)depositing one or more solid build inks in a plurality of build inklayers to form the three-dimensional article on a substrate, eachdeposited build ink layer of the plurality of build ink layers beingdisposed on (a) the substrate, (b) a portion of a previous solid buildink layer, (c) a portion of the one or more scaffold layers, or (d)combinations thereof, (4) depositing the support material in the one ormore scaffold layers, each deposited scaffold layer being disposed on(a) the substrate, (b) a portion of a previous solid build ink layer,(c) a portion of the one or more scaffold layers, or (d) combinationsthereof, and (5) curing each of the plurality of build ink layers toform the three-dimensional article.

In some aspects, embodiments herein provide sets of solid build inks foruse in color three-dimensional printing, each of the set of solid buildinks comprising a solid acrylate in an amount from about 40 to about 70percent by weight, a non-curable wax in an amount from about 10 to about45 percent by weight a curable wax in an amount from about 1 to about 15percent by weight; a photoinitiator; and a colorant, wherein each solidbuild ink in the set has a different colorant and has a curing speedadjusted by a ratio of the non-curable wax to curable wax such that thecuring speed and final hardness of each solid build ink is substantiallythe same independent of the colorant in a given solid build ink.

BRIEF DESCRIPTION OF DRAWINGS

Various embodiments of the present disclosure will be described hereinbelow with reference to the figures wherein:

FIG. 1 shows a plot of complex viscosity versus temperature forexemplary cyan solid build inks, in accordance with embodiments herein.

FIG. 2 shows a plot of the curing profile of the exemplary solid buildinks of FIG. 1 prior to addition of colorant.

FIG. 3 shows a plot of initial slope versus initial hardness for avariety of solid build inks in accordance with embodiments herein.

DETAILED DESCRIPTION

Embodiments herein provide conditions for a set of solid build inks foruse in three-dimensional printing. The solid build inks are UV curableinks (no liquid components) and are readily tailored to fit thespecifications for compatibility with current three-dimensional inkjetprinting systems. The solid build inks offer many advantages overconventional UV curable build inks known in the art, such as those basedon urethane resin and wax systems described, for example, in U.S. Pat.Nos. 7,378,460 and 6,841,589.

The solid build inks disclosed herein are designed for easy colorantincorporation to provide a wide variety of colors and the ability toprint layers from about 10 microns up to about 5 mm in thickness beforecuring. In particular, the solid build inks are flexible in design toaccount for differences in initial hardness and cure rates such thateach color of a set of solid build inks can be modified to synchronizecure times and final hardness thereby avoiding potential issues withuneven shrinkage and cure rates across different colors.

In the selective deposition methods disclosed herein, a curable solidbuild ink may be jetted onto a non-curable wax support material;optionally this non-curable wax may be a variant of the curable solidink without photoinitiator(s). Although typically the supporting waxwill be the same wax that is used to formulate the solid build ink foreconomy of material and methodology, there is no strict requirement thatthey be the same. Each layer is cured after each deposition oralternatively after multiple passes or in some embodiments, the cureoccurs only once the full three-dimensional object has been fabricated.When the fabrication is complete, the support material may be washed,melted or blasted away from the 3D fabrication, depending on thecomposition of the support material.

The UV curable solid build inks disclosed herein may generally have thefollowing properties when employed in conjunction with jet printingsystems: (1) they are jettable with a viscosity of about 8 to about 16cps at temperatures between about 70° C. and 95° C.; (2) they are softsolids at temperatures below about 30° C. prior to curing; and (3) theyexhibit high curing rates upon exposure to UV irradiation.

In embodiments, all of the solid build ink components (i.e., monomers,photoinitiators, and the like) are solid at ambient temperature. Thesesolid build inks have the added advantage of being easily pigmented andtheir phase change properties make them suitable for printing onvirtually any substrate, including, porous support materials.Additionally, as mentioned above, the solid build inks can be printed inone pass to the desired 3D dimension without intervening printing/curingsteps in conventional 3D processes. These and other advantages will beapparent to those skilled in the art.

In embodiments, there are provided color 3D printing systems comprisinga solid build ink for each of a plurality of colors, each solid buildink comprising a solid acrylate in an amount from about 55 to about 95percent by weight, a non-curable wax in an amount from about 5 to about45 percent, a curable wax in an amount from about 0.1 to about 30percent, a photoinitiator; and a colorant, wherein each solid build inkhas a curing speed adjusted by a ratio of the non-curable wax to curablewax such that the curing speed and final hardness of each solid buildink is approximately the same for each of the plurality of colors, thesystems further comprising a support material comprising the non-curablewax used in each build ink, the support material providing a scaffoldfor deposition of each build ink. The support material is generallybuilt up via the same printing mechanism by which the solid build ink isdeposited.

The present embodiments provide low energy ultraviolet (UV) curablepigmented solid build inks with high reactivity and minimum shrinkagefor application in three-dimensional printing. These solid build inksmay optionally contain a gellant additive and may be formulated withviscosities in the range of less than 20 cPs at 90° C., or from about 20to about 5 cPS at 90° C., or from about 15 to about 8 cPs at 90° C., anda shrinkage value of less than 3%, or from about 1 to about 3%. As usedherein, the shrinkage value indicates the shrinkage of the ink uponcooling from a liquid state. In addition, these inks exhibit a hardnessafter curing much higher than conventional solid inks, such as thosecommercially available from Xerox Corporation or Océ North America.Tuneability in curing rate and final hardness after curing was alsoshown for these solid build inks as well as improved compatibilitybetween components upon solidification. Curing rates can be obtained byplotting the hardness versus duration of exposure to UV light in ft/s(feet per second) (Fusions UV doped mercury D-bulb, 600 W/cm) andapplying the following expressions:

y=m ₁ +m ₂·(1−exp(−m ₃ ·x))

Initial Hardness=m₁

Initial Slope=m ₂ ·m ₃

Final Hardness=m ₁ +m ₂

where the initial slope is taken as the initial curing rate. The solidbuild inks herein may display curing rates from about 130 to about 250ft/s, such as from about 180 to about 250 ft/s or from about 200 toabout 250 ft/s. Depending on the type of bulb used in the UV curablelamp, the characteristic output used for curing may be from about 200 nmto about 450 nm.

The solid build inks may comprise blends of curable waxes, non-curablewaxes, monomers, optional gellants, colorants, and free-radicalphotoinitiators, and optionally up to 5 percent by weight of non-curableresins, such as viscosity modifiers. The various components are solidmaterials below about 40° C., or from below about 40° C. to below about30° C. These components were selected to achieve jetting at temperaturesin the range of from about 70° C. to about 100° C., or from about 80° C.to about 100° C., or from about 70° C. to about 90° C. These solid buildinks thus have robust jetting at elevated temperatures with a viscosityof from about 5 to about 15 cPs, or from about 10 to about 15 cPs, orfrom about 8 to about 12 cPs at these temperatures, and are solid atroom temperature which prevents excessive spreading or migration of theprinted droplet on, for example, porous substrates. After printing oneor more layers in the construction of a three-dimensional article, thecompositions are cured to provide robust articles.

The curable solid build inks may have a pre-cured hardness of from about0.1 to about 50 or of from about 5 to about 50, or of from about 10 toabout 50. These inks may have a post-cured hardness of from about 70 toabout 100, or of from about 80 to about 97, or of from about 80 to about95. One skilled in the art will recognize that these are Shore Durometerhardness values and that durometer values are dimensionless quantities.

The curable solid build ink components may include monomers, curablewaxes and optionally gellants. The curable wax may be a solid at roomtemperature (about 25° C.). Inclusion of the wax may promote an increasein viscosity of the solid build ink as the composition cools from theapplication temperature. The curable wax may be any wax component thatis miscible with the other components and that will polymerize to form apolymer. The term wax includes, for example, any of the various natural,modified natural, and synthetic materials commonly referred to as waxes.

Suitable examples of curable waxes include waxes that include or arefunctionalized with curable groups. The curable groups may include, forexample, an acrylate, methacrylate, alkene, allylic ether, epoxide,oxetane, and the like. These waxes can be synthesized by the reaction ofa wax, such as a polyethylene wax equipped with a carboxylic acid orhydroxyl transformable functional group. The curable waxes describedherein may be cured with the above isosorbide functionalized with atleast one curable group and/or the additional curable monomer(s).

Suitable examples of hydroxyl-terminated polyethylene waxes that may befunctionalized with a curable group include mixtures of carbon chainswith the structure CH₃—(CH₂)—CH₂OH, where there is a mixture of chainlengths, n, where the average chain length can be in the range of about16 to about 50, and linear low molecular weight polyethylene, of similaraverage chain length. Suitable examples of such waxes include, but arenot limited to, the UNILIN series of materials such as UNILIN 350,UNILIN 425, UNILIN 550 and UNILIN 700 with M_(n) approximately equal to375, 460, 550 and 700 g/mol, respectively. All of these waxes arecommercially available from Baker-Petrolite. Guerbet alcohols,characterized as 2,2-dialkyl-1-ethanols, are also suitable compounds.Exemplary Guerbet alcohols include those containing about 16 to about 36carbons, many of which are commercially available from JarchemIndustries Inc., Newark, N.J. PRIPOL® 2033 (C-36 dimer diol mixtureincluding isomers of the formula

as well as other branched isomers that may include unsaturations andcyclic groups, available from Uniqema, New Castle, Del.; furtherinformation on C₃₆ dimer diols of this type is disclosed in, forexample, “Dimer Acids,” Kirk-Othmer Encyclopedia of Chemical Technology,Vol. 8, 4^(th) Ed. (1992), pp. 223-237, the disclosure of which istotally incorporated herein by reference, may also be used. Thesealcohols can be reacted with carboxylic acids equipped with UV curablemoieties to form reactive esters. Examples of these acids includeacrylic and methacrylic acids, available from Sigma-Aldrich Co.

Suitable examples of carboxylic acid-terminated polyethylene waxes thatmay be functionalized with a curable group include mixtures of carbonchains with the structure CH₃—(CH₂)—COON, where there is a mixture ofchain lengths, n, where the average chain length is about 16 to about50, and linear low molecular weight polyethylene, of similar averagechain length. Suitable examples of such waxes include UNICID® 350,UNICID® 425, UNICID® 550 and UNICID® 700 with M_(n) equal toapproximately 390, 475, 565 and 720 g/mol, respectively. Other suitablewaxes have a structure CH₃—(CH₂)—COOH, such as hexadecanoic or palmiticacid with n=14, heptadecanoic or margaric or daturic acid with n=15,octadecanoic or stearic acid with n=16, eicosanoic or arachidic acidwith n=18, docosanoic or behenic acid with n=20, tetracosanoic orlignoceric acid with n=22, hexacosanoic or cerotic acid with n=24,heptacosanoic or carboceric acid with n=25, octacosanoic or montanicacid with n=26, triacontanoic or melissic acid with n=28,dotriacontanoic or lacceroic acid with n=30, tritriacontanoic orceromelissic or psyllic acid, with n=31, tetratriacontanoic or geddicacid with n=32, pentatriacontanoic or ceroplastic acid with n=33.Guerbet acids, characterized as 2,2-dialkyl ethanoic acids, are alsosuitable compounds. Exemplary Guerbet acids include those containing 16to 36 carbons, many of which are commercially available from JarchemIndustries Inc., Newark, N.J. PRIPOL® 1009 (C-36 dimer acid mixtureincluding isomers of the formula

as well as other branched isomers that may include unsaturations andcyclic groups, available from Uniqema, New Castle, Del.; furtherinformation on C₃₆ dimer acids of this type is disclosed in, forexample, “Dimer Acids,” Kirk-Othmer Encyclopedia of Chemical Technology,Vol. 8, 4^(th) Ed. (1992), pp. 223-237, the disclosure of which istotally incorporated herein by reference, can also be used. Thesecarboxylic acids can be reacted with alcohols equipped with UV curablemoieties to form reactive esters. Examples of these alcohols include,but are not limited to, 2-allyloxyethanol from Sigma-Aldrich Co.;

SR495B from Sartomer Company, Inc. (Exton, Pa.); and

CD572 (R═H, n=10) and SR604 (R═Me, n=4) from Sartomer Company, Inc.

The curable wax can be included in the solid build inks in an amount offrom, for example, about 0.1% to about 30% by weight of the composition,such as from about 0.5% to about 20% or from about 0.5% to 15% by weightof the composition.

The monomers that may be used in the present embodiments are, inembodiments, those described in U.S. Pat. No. 7,559,639, which is herebyincorporated by reference. For example, the monomer may be a dimethanoldiacrylate cyclohexane difunctional monomer, such as for example, CD-406from Sartomer (mp=78° C.); an isocyanurate triacrylate trifunctionalmonomer, such as for example, SR-368 from Sartomer (mp=50-55° C.); abehenyl acrylate monofunctional mionomer C18,C20,C22 mixture, such asfor example, CD587 from Sartomer (mp=55° C.); an acrylate curablemonofunctional acrylate wax C22,C23,C24 mixture, such as for example,UNILIN 350 from Baker Petrolite (Houston, Tex.) (mp=78-83° C.); andoptionally a curable amide gellant.

The optional gellants suitable for use in the radiation curable solidbuild ink may include a gellant comprised of a curable amide, a curablepolyamide-epoxy acrylate component, a polyamide component, mixturesthereof and the like. In further embodiments, a curable compositegellant may be comprised of a curable epoxy resin and a polyamide resin,mixtures thereof and the like. The gellant may also participate in thecuring of monomer(s) in the composition. The gellants suitable for usein the solid inks may be amphiphilic in nature in order to improvewetting when the ink composition is utilized over a substrate havingsilicone or other oil thereon. Amphiphilic refers to molecules that haveboth polar and non-polar parts of the molecule. For example, thegellants may have long non-polar hydrocarbon chains and polar amidelinkages.

Amide gellants suitable for use include those described in U.S. PatentApplication Publication No. 2008/0122914 and U.S. Pat. Nos. 7,276,614and 7,279,587, the entire disclosures of which are incorporated hereinby reference. However, unlike the present embodiments, which are solidcurable inks at room temperature both in the presence and absence of agellant, the above patents are directed to liquid curable inks. Inspecific embodiments, the gellant is a mixture of components that alsoincludes both curable and non-curable gellants.

In embodiments, the solid build inks are formulated with a gellantmaterial. Gellants suitable for use in the ink compositions include agellant comprised of a curable amide, a curable polyamide-epoxy acrylatecomponent and a polyamide component, a curable composite gellantcomprised of a curable epoxy resin and a polyamide resin, mixturesthereof and the like, as disclosed in U.S. patent application Ser. No.12/474,946, which is hereby incorporated herein by reference in itsentirety. The gellant may also participate in the curing of monomer(s)of the composition.

The gellants suitable for use in the solid build ink may be amphiphilicin nature in order to improve wetting when the composition is utilizedover a substrate having silicone or other oil thereon. Amphiphilicrefers to molecules that have both polar and non-polar parts of themolecule. For example, the gellants may have long non-polar hydrocarbonchains and polar amide linkages. Amide gellants suitable for use includethose described in U.S. Patent Application Publication No. 2008/0122914and U.S. Pat. Nos. 7,276,614 and 7,279,587, the entire disclosures ofwhich are incorporated herein by reference. Additional gellants suitablefor use also include those described in U.S. patent application Ser. No.12/765,148 to Chopra et al. filed on Apr. 22, 2010. As described in U.S.Pat. No. 7,279,587, the amide gellant may be a compound of the formula

wherein:

R₁ is:

(i) an alkylene group (wherein an alkylene group is a divalent aliphaticgroup or alkyl group, including linear and branched, saturated andunsaturated, cyclic and acyclic, and substituted and unsubstitutedalkylene groups, and wherein heteroatoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in the alkylene group) having from about 1 carbon atom toabout 12 carbon atoms, such as from about 1 carbon atom to about 8carbon atoms or from about 1 carbon atom to about 5 carbon atoms,

(ii) an arylene group (wherein an arylene group is a divalent aromaticgroup or aryl group, including substituted and unsubstituted arylenegroups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, boron, and the like either may or may not bepresent in the arylene group) having from about 1 carbon atom to about15 carbon atoms, such as from about 3 carbon atoms to about 10 carbonatoms or from about 5 carbon atoms to about 8 carbon atoms,

(iii) an arylalkylene group (wherein an arylalkylene group is a divalentarylalkyl group, including substituted and unsubstituted arylalkylenegroups, wherein the alkyl portion of the arylalkylene group can belinear or branched, saturated or unsaturated, and cyclic or acyclic, andwherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, boron, and the like either may or may not be present ineither the aryl or the alkyl portion of the arylalkylene group) havingfrom about 6 carbon atoms to about 32 carbon atoms, such as from about 6carbon atoms to about 22 carbon atoms or from about 6 carbon atoms toabout 12 carbon atoms, or

(iv) an alkylarylene group (wherein an alkylarylene group is a divalentalkylaryl group, including substituted and unsubstituted alkylarylenegroups, wherein the alkyl portion of the alkylarylene group can belinear or branched, saturated or unsaturated, and cyclic or acyclic, andwherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, boron, and the like either may or may not be present ineither the aryl or the alkyl portion of the alkylarylene group) havingfrom about 5 carbon atoms to about 32 carbon atoms, such as from about 6carbon atoms to about 22 carbon atoms or from about 7 carbon atoms toabout 15 carbon atoms,

wherein the substituents on the substituted alkylene, arylene,arylalkylene, and alkylarylene groups can be halogen atoms, cyanogroups, pyridine groups, pyridinium groups, ether groups, aldehydegroups, ketone groups, ester groups, amide groups, carbonyl groups,thiocarbonyl groups, sulfide groups, nitro groups, nitroso groups, acylgroups, azo groups, urethane groups, urea groups, mixtures thereof, andthe like, wherein two or more substituents can be joined together toform a ring;

R₂ and R₂′ each, independently of the other, are:

-   -   (i) alkylene groups having from about 1 carbon atom to about 54        carbon atoms, such as from about 1 carbon atom to about 48        carbon atoms or from about 1 carbon atom to about 36 carbon        atoms,    -   (ii) arylene groups having from about 5 carbon atoms to about 15        carbon atoms, such as from about 5 carbon atoms to about 13        carbon atoms or from about 5 carbon atoms to about 10 carbon        atoms,    -   (iii) arylalkylene groups having from about 6 carbon atoms to        about 32 carbon atoms, such as from about 7 carbon atoms to        about 33 carbon atoms or from about 8 carbon atoms to about 15        carbon atoms, or    -   (iv) alkylarylene groups having from about 6 carbon atoms to        about 32 carbon atoms, such as from about 6 carbon atoms to        about 22 carbon atoms or from about 7 carbon atoms to about 15        carbon atoms,        wherein the substituents on the substituted alkylene, arylene,        arylalkylene, and alkylarylene groups may be halogen atoms,        cyano groups, ether groups, aldehyde groups, ketone groups,        ester groups, amide groups, carbonyl groups, thiocarbonyl        groups, phosphine groups, phosphonium groups, phosphate groups,        nitrile groups, mercapto groups, nitro groups, nitroso groups,        acyl groups, acid anhydride groups, azide groups, azo groups,        cyanato groups, urethane groups, urea groups, mixtures thereof,        and the like, and wherein two or more substituents may be joined        together to form a ring;

-   R₃ and R₃′ each, independently of the other, are either:    -   (a) photoinitiating groups, such as groups derived from        1-(4-(2-hydroxyethoxy)phenyl)-2-hydroxy-2-methylpropan-1-one, of        the formula

groups derived from 1-hydroxycyclohexylphenylketone, of the formula

groups derived from 2-hydroxy-2-methyl-1-phenylpropan-1-one, of theformula

groups derived from N,N-dimethylethanolamine orN,N-dimethylethylenediamine, of the formula

-   or the like, or:

-   -   (b) a group which is:        -   (i) an alkyl group (including linear and branched, saturated            and unsaturated, cyclic and acyclic, and substituted and            unsubstituted alkyl groups, and wherein heteroatoms, such as            oxygen, nitrogen, sulfur, silicon, phosphorus, boron, and            the like either may or may not be present in the alkyl            group) having from about 2 carbon atoms to about 100 carbon            atoms, such as from about 3 carbon atoms to about 60 carbon            atoms or from about 4 carbon atoms to about 30 carbon atoms,        -   (ii) an aryl group (including substituted and unsubstituted            aryl groups, and wherein heteroatoms, such as oxygen,            nitrogen, sulfur, silicon, phosphorus, boron, and the like            either may or may not be present in the aryl group) having            from about 5 carbon atoms to about 100 carbon atoms, such as            from about 5 carbon atoms to about 60 carbon atoms or from            about 6 carbon atoms to about 30 carbon atoms, such as            phenyl or the like,        -   (iii) an arylalkyl group (including substituted and            unsubstituted arylalkyl groups, wherein the alkyl portion of            the arylalkyl group can be linear or branched, saturated or            unsaturated, and cyclic or acyclic, and wherein heteroatoms,            such as oxygen, nitrogen, sulfur, silicon, phosphorus,            boron, and the like either may or may not be present in            either the aryl or the alkyl portion of the arylalkyl group)            having from about 5 carbon atoms to about 100 carbon atoms,            such as from about 5 carbon atoms to about 60 carbon atoms            or from about 6 carbon atoms to about 30 carbon atoms, such            as benzyl or the like, or        -   (iv) an alkylaryl group (including substituted and            unsubstituted alkylaryl groups, wherein the alkyl portion of            the alkylaryl group can be linear or branched, saturated or            unsaturated, and cyclic or acyclic, and wherein heteroatoms,            such as oxygen, nitrogen, sulfur, silicon, phosphorus,            boron, and the like either may or may not be present in            either the aryl or the alkyl portion of the alkylaryl group)            having from about 5 carbon atoms to about 100 carbon atoms,            such as from about 5 carbon atoms to about 60 carbon atoms            or from about 6 carbon atoms to about 30 carbon atoms, such            as tolyl or the like,            wherein the substituents on the substituted alkyl,            arylalkyl, and alkylaryl groups may be halogen atoms, ether            groups, aldehyde groups, ketone groups, ester groups, amide            groups, carbonyl groups, thiocarbonyl groups, sulfide            groups, phosphine groups, phosphonium groups, phosphate            groups, nitrile groups, mercapto groups, nitro groups,            nitroso groups, acyl groups, acid anhydride groups, azide            groups, azo groups, cyanato groups, isocyanato groups,            thiocyanato groups, isothiocyanato groups, carboxylate            groups, carboxylic acid groups, urethane groups, urea            groups, mixtures thereof, and the like, and wherein two or            more substituents may be joined together to form a ring; and            X and X′ each, independently of the other, is an oxygen atom            or a group of the formula —NR₄—, wherein R₄ is:

-   (i) a hydrogen atom;

-   (ii) an alkyl group, including linear and branched, saturated and    unsaturated, cyclic and acyclic, and substituted and unsubstituted    alkyl groups, and wherein heteroatoms either may or may not be    present in the alkyl group, having from about 5 carbon atoms to    about 100 carbon atoms, such as from about 5 carbon atoms to about    60 carbon atoms or from about 6 carbon atoms to about 30 carbon    atoms,

-   (iii) an aryl group, including substituted and unsubstituted aryl    groups, and wherein heteroatoms either may or may not be present in    the aryl group, having from about 5 carbon atoms to about 100 carbon    atoms, such as from about 5 carbon atoms to about 60 carbon atoms or    from about 6 carbon atoms to about 30 carbon atoms,

-   (iv) an arylalkyl group, including substituted and unsubstituted    arylalkyl groups, wherein the alkyl portion of the arylalkyl group    may be linear or branched, saturated or unsaturated, and cyclic or    acyclic, and wherein heteroatoms either may or may not be present in    either the aryl or the alkyl portion of the arylalkyl group, having    from about 5 carbon atoms to about 100 carbon atoms, such as from    about 5 carbon atoms to about 60 carbon atoms or from about 6 carbon    atoms to about 30 carbon atoms, or

-   (v) an alkylaryl group, including substituted and unsubstituted    alkylaryl groups, wherein the alkyl portion of the alkylaryl group    can be linear or branched, saturated or unsaturated, and cyclic or    acyclic, and wherein heteroatoms either may or may not be present in    either the aryl or the alkyl portion of the alkylaryl group, having    from about 5 carbon atoms to about 100 carbon atoms, such as from    about 5 carbon atoms to about 60 carbon atoms or from about 6 carbon    atoms to about 30 carbon atoms,    wherein the substituents on the substituted alkyl, aryl, arylalkyl,    and alkylaryl groups may be halogen atoms, ether groups, aldehyde    groups, ketone groups, ester groups, amide groups, carbonyl groups,    thiocarbonyl groups, sulfate groups, sulfonate groups, sulfonic acid    groups, sulfide groups, sulfoxide groups, phosphine groups,    phosphonium groups, phosphate groups, nitrile groups, mercapto    groups, nitro groups, nitroso groups, sulfone groups, acyl groups,    acid anhydride groups, azide groups, azo groups, cyanato groups,    isocyanato groups, thiocyanato groups, isothiocyanato groups,    carboxylate groups, carboxylic acid groups, urethane groups, urea    groups, mixtures thereof, and the like, and wherein two or more    substituents may be joined together to form a ring.

Specific suitable substituents and gellants of the above are further setforth in U.S. Pat. Nos. 7,279,587 and 7,276,614, incorporated herein byreference in their entireties. In embodiments, the gellant may comprisea mixture comprising:

wherein —C₃₄H_(56+a)— represents a branched alkylene group which mayinclude unsaturations and cyclic groups, wherein the variable “a” is aninteger from 0-12.

In embodiments, the gellant may be one of the aromatic end-cappedgellants described in U.S. patent application Ser. No. 12/765,148 toChopra et al. filed on Apr. 22, 2010, which is hereby incorporated byreference in its entirety. In embodiments, the gellants of the ink maybe compounds with the following general structures

As mentioned above, the solid build ink can include the optional gellingagent, or gellant, in any suitable amount, such as about 1 percent toabout 50 percent or from about 2 percent to about 20 percent or fromabout 5 percent to about 15 percent by weight of the ink.

The non-curable solid components of the solid build ink may includenon-curable waxes including ethoxylated octylphenol derivatives, whichare soluble in the ink composition and/or have a melting point of about5° C. to about 10° C. below jetting temperatures (which may range fromabout 70° C. to about 100° C.) so that the non-curable waxeshomogenously combine with the other components of the solid build inkcomposition. Furthermore, the molecular weight (MW) of ethoxylatedoctylphenol derivatives range from about 600 to about 5000 g/mole.

Reactants for the ethoxylated octylphenol derivatives may be selectedfrom the Triton and IGEPAL CA series based on octylphenol ethoxylates,such as for example, IGEPAL CA-210 (equivalent to Triton X-15), IGEPALCA-420 (equivalent to Triton X-35), IGEPAL CA-510 (equivalent to TritonX-45), IGEPAL CA-620 (equivalent to Triton X-114), IGEPAL CA-630(equivalent to Triton X-100), IGEPAL CA-720 (equivalent to TritonX-102), IGEPAL CA-887 (equivalent to Triton X-305), IGEPAL CA-890(equivalent to Triton X-405), IGEPAL CA-897 (equivalent to TritonX-705), as well as IGEPAL CO series (based on nonylphenol ethoxylation)such as IGEPAL CO210, IGEPAL CO520, IGEPAL CO630, IGEPAL CO720, IGEPALCO890, and IGEPAL DM970 based on dinonylphenol ethoxylates.

The ethoxylated octylphenol derivatives may be prepared by mixingspecific reactive components, for example, an ethoxylated octylphenol, alinear alcohol, and a diisocyanate and/or a polyisocyanate. Thesereactive components may include a linear alcohol having 38 or 30 carbons(sold under the tradename UNILIN 425); ethoxylated octylphenols, such asIGEPAL CA-210, IGEPAL CA-420, IGEPAL CA-520, IGEPAL CA-620, IGEPALCA-630, and IGEPAL CA-720 (ethoxylated octylphenols sold under thetradename IGEPAL; formally manufactured by Rhone-Poulene Co. andcurrently manufactured by Rhodia; the Triton Series was formallymanufactured by Union Carbide and currently manufactured by the DowChemical Company); diisocyanates and polyisocyanates, includingaromatic, aliphatic, cycloaliphatic and/or (cyclo)aliphaticdiisocyanates and/or polyisocyanates. Suitable aliphatic diisocyanatesor polyisocyanates may have 3 to 16 carbon atoms or 4 to 12 carbonatoms, in the linear or branched alkyl portion, and suitablecycloaliphatic or (cyclo)aliphatic diisocyanates may possess 4 to 18carbon atoms or 6 to 15 carbon atoms, in the cylcoalkyl portion. Theterm “(cyclo)aliphatic diisocyanates” refers, for example, to NCO groupsthat are attached cyclically and aliphatically at the same time (such asisophorone diisocyanate); and cycloaliphatic diisocyanates include thosewhich contain only NCO groups attached directly to the cycloaliphaticring, such as H₁₂MDI. Suitable diisocyanates and polyisocyanatesinclude, for example, those that are listed in U.S. patent applicationSer. No. 12/704,194 to Breton et al., which is hereby incorporated byreference.

The solid build inks may be formulated using non-curable components andboth commercial resin Licowax-KFO and the IGEPAL custom materials. Inone embodiment, the non-curable component of the present embodiments,present in the range of 0 to 25 percent by weight in the ink, is anIGEPAL CA210 derivative or mixture of IGEPAL CA210 derivatives. Specificembodiments used the TMHDI and IPDI derivatives, melting respectively at87° C. and 88° C.

The solid build inks may also contain a colorant. Any desired oreffective colorant can be employed in the ink compositions, includingdyes, pigments, mixtures thereof, and the like, provided that thecolorant can be dissolved or dispersed in the ink vehicle and iscompatible with the other ink components. Pigments, which are typicallycheaper and more robust than dyes, may be included in the curable solidbuild ink. The color of many dyes can be altered by the polymerizationprocess occurring during the curing stage, presumably from attack oftheir molecular structure by the free radicals. The compositions can beused in combination with conventional ink-colorant materials, such asColor Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acid and DirectDyes, Basic Dyes, Sulphur Dyes, Vat Dyes, and the like.

Examples of suitable dyes include Neozapon Red 492 (BASF); Orasol Red G(Ciba); Direct Brilliant Pink B (Oriental Giant Dyes); Direct Red 3BL(Classic Dyestuffs); Supranol Brilliant Red 3BW (Bayer AG); Lemon Yellow6G (United Chemie); Light Fast Yellow 3G (Shaanxi); Aizen Spilon YellowC-GNH (Hodogaya Chemical); Bernachrome Yellow GD Sub (ClassicDyestuffs); Cartasol Brilliant Yellow 4GF (Clariant); Cibanon Yellow 2GN(Ciba); Orasol Black CN (Ciba); Savinyl Black RLSN (Clariant); PyrazolBlack BG (Clariant); Morfast Black 101 (Rohm & Haas); Diaazol Black RN(ICI); Orasol Blue GN (Ciba); Savinyl Blue GLS (Clariant); Luxol FastBlue MBSN (Pylam Products); Sevron Blue 5GMF (Classic Dyestuffs);Basacid Blue 750 (BASF), Neozapon Black X51 (BASF), Classic SolventBlack 7 (Classic Dyestuffs), Sudan Blue 670 (C.I. 61554) (BASF), SudanYellow 146 (C.I. 12700) (BASF), Sudan Red 462 (C.I. 26050) (BASF), C.I.Disperse Yellow 238, Neptune Red Base NB543 (BASF, C.I. Solvent Red 49),Neopen Blue FF-4012 from BASF, Lampronol Black BR from ICI (C.I. SolventBlack 35), Morton Morplas Magenta 36 (C.I. Solvent Red 172), metalphthalocyanine colorants such as those disclosed in U.S. Pat. No.6,221,137, the disclosure of which is incorporated herein by referencein its entirety. Polymeric dyes can also be used, such as thosedisclosed in, for example, U.S. Pat. No. 5,621,022 and U.S. Pat. No.5,231,135, the disclosures of each of which are herein entirelyincorporated herein by reference, and commercially available from, forexample, Milliken & Company as Milliken Ink Yellow 869, Milliken InkBlue 92, Milliken Ink Red 357, Milliken Ink Yellow 1800, Milliken InkBlack 8915-67, uncut Reactant Orange X-38, uncut Reactant Blue X-17,Solvent Yellow 162, Acid Red 52, Solvent Blue 44, and uncut ReactantViolet X-80.

Pigments are also suitable colorants for the curable phase change inks.Examples of suitable pigments include PALIOGEN Violet 5100 (commerciallyavailable from BASF); PALIOGEN Violet 5890 (commercially available fromBASF); HELIOGEN Green L8730 (commercially available from BASF); LITHOLScarlet D3700 (commercially available from BASF); SUNFAST Blue 15:4(commercially available from Sun Chemical); Hostaperm Blue B2G-D(commercially available from Clariant); Hostaperm Blue B4G (commerciallyavailable from Clariant); Permanent Red P-F7RK; Hostaperm Violet BL(commercially available from Clariant); LITHOL Scarlet 4440(commercially available from BASF); Bon Red C (commercially availablefrom Dominion Color Company); ORACET Pink RF (commercially availablefrom Ciba); PALIOGEN Red 3871 K (commercially available from BASF);SUNFAST Blue 15:3 (commercially available from Sun Chemical); PALIOGENRed 3340 (commercially available from BASF); SUNFAST Carbazole Violet 23(commercially available from Sun Chemical); LITHOL Fast Scarlet L4300(commercially available from BASF); SUNBRITE Yellow 17 (commerciallyavailable from Sun Chemical); HELIOGEN Blue L6900, L7020 (commerciallyavailable from BASF); SUNBRITE Yellow 74 (commercially available fromSun Chemical); SPECTRA PAC C Orange 16 (commercially available from SunChemical); HELIOGEN Blue K6902, K6910 (commercially available fromBASF); SUNFAST Magenta 122 (commercially available from Sun Chemical);HELIOGEN Blue D6840, D7080 (commercially available from BASF); SudanBlue OS (commercially available from BASF); NEOPEN Blue FF4012(commercially available from BASF); PV Fast Blue 82001 (commerciallyavailable from Clariant); IRGALITE Blue BCA (commercially available fromCiba); PALIOGEN Blue 6470 (commercially available from BASF); SudanOrange G (commercially available from Aldrich), Sudan Orange 220(commercially available from BASF); PALIOGEN Orange 3040 (BASF);PALIOGEN Yellow 152, 1560 (commercially available from BASF); LITHOLFast Yellow 0991 K (commercially available from BASF); PALIOTOL Yellow1840 (commercially available from BASF); NOVOPERM Yellow FGL(commercially available from Clariant); Ink Jet Yellow 4G VP2532(commercially available from Clariant); Toner Yellow HG (commerciallyavailable from Clariant); Lumogen Yellow D0790 (commercially availablefrom BASF); Suco-Yellow L1250 (commercially available from BASF);Suco-Yellow DI355 (commercially available from BASF); Suco Fast YellowDI355, DI351 (commercially available from BASF); HOSTAPERM Pink E 02(commercially available from Clariant); Hansa Brilliant Yellow 5GX03(commercially available from Clariant); Permanent Yellow GRL 02(commercially available from Clariant); Permanent Rubine L6B 05(commercially available from Clariant); FANAL Pink D4830 (commerciallyavailable from BASF); CINQUASIA Magenta (commercially available from DUPONT); PALIOGEN Black L0084 (commercially available from BASF); PigmentBlack K801 (commercially available from BASF); and carbon blacks such asREGAL 330™ (commercially available from Cabot), Nipex 150 (commerciallyavailable from Degusssa) Carbon Black 5250 and Carbon Black 5750(commercially available from Columbia Chemical), and the like, as wellas mixtures thereof.

Also suitable are the colorants disclosed in U.S. Pat. No. 6,472,523,U.S. Pat. No. 6,726,755, U.S. Pat. No. 6,476,219, U.S. Pat. No.6,576,747, U.S. Pat. No. 6,713,614, U.S. Pat. No. 6,663,703, U.S. Pat.No. 6,755,902, U.S. Pat. No. 6,590,082, U.S. Pat. No. 6,696,552, U.S.Pat. No. 6,576,748, U.S. Pat. No. 6,646,111, U.S. Pat. No. 6,673,139,U.S. Pat. No. 6,958,406, U.S. Pat. No. 6,821,327, U.S. Pat. No.7,053,227, U.S. Pat. No. 7,381,831 and U.S. Pat No. 7,427,323, thedisclosures of each of which are incorporated herein by reference intheir entirety.

In embodiments, solvent dyes may be employed. An example of a solventdye suitable for use herein may include spirit soluble dyes because oftheir compatibility with the ink carriers disclosed herein. Examples ofsuitable spirit solvent dyes include Neozapon Red 492 (BASF); Orasol RedG (Ciba); Direct Brilliant Pink B (Global Colors); Aizen Spilon Red C-BH(Hodogaya Chemical); Kayanol Red 3BL (Nippon Kayaku); Spirit Fast Yellow3G; Aizen Spilon Yellow C-GNH (Hodogaya Chemical); Cartasol BrilliantYellow 4GF (Clariant); Pergasol Yellow CGP (Ciba); Orasol Black RLP(Ciba); Savinyl Black RLS (Clariant); Morfast Black Conc. A (Rohm andHaas); Orasol Blue GN (Ciba); Savinyl Blue GLS (Sandoz); Luxol Fast BlueMBSN (Pylam); Sevron Blue 5GMF (Classic Dyestuffs); Basacid Blue 750(BASF), Neozapon Black X51 [C.I. Solvent Black, C.I. 12195] (BASF),Sudan Blue 670 [C.I. 61554] (BASF), Sudan Yellow 146 [C.I. 12700](BASF), Sudan Red 462 [C.I. 260501] (BASF), mixtures thereof and thelike.

The colorant may be present in the solid build ink in any desired oreffective amount to obtain the desired color or hue such as, forexample, at least from about 0.1 percent by weight of the ink to about30 percent by weight of the ink, or from at least from about 0.2 percentby weight of the ink to about 20 percent by weight of the ink, or atleast from about 0.5 percent by weight of the ink to about 10 percent byweight of the ink.

The curable solid build ink may optionally include an initiator, suchas, for example, a photoinitiator. Such an initiator is desirable forassisting in curing of the solid build ink. In embodiments, aphotoinitiator that absorbs radiation, for example UV light radiation,to initiate curing of the curable components of the solid build ink. Asthe photoinitiator for solid build ink that are cured by free-radicalpolymerization, for instance, ink compositions containing acrylategroups or inks comprised of polyamides, mentioned above may be made ofphotoinitiators such as benzophenones, benzoin ethers, benzil ketals,α-hydroxyalkylphenones, α-alkoxyalkylphenones α-aminoalkylphenones andacylphosphine photoinitiators sold under the trade designations ofIRGACURE and DAROCUR from Ciba. Specific examples of suitablephotoinitiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide(available as BASF LUCIRIN TPO);2,4,6-trimethylbenzoylethoxyphenylphosphine oxide (available as BASFLUCIRIN TPO-L); bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide(available as Ciba IRGACURE 819) and other acyl phosphines;2-methyl-1-(4-methylthio)phenyl-2-(4-morphorlinyl)-1-propanone(available as Ciba IRGACURE 907) and1-(4-(2-hydroxyethoxy)phenyl)-2-hydroxy-2-methylpropan-1-one (availableas Ciba IRGACURE 2959); 2-benzyl 2-dimethylamino1-(4-morpholinophenyl)butanone-1 (available as Ciba IRGACURE 369);2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)-benzyl)-phenyl)-2-methylpropan-1-one(availableas Ciba IRGACURE 127);2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butanone(availableas Ciba IRGACURE 379); titanocenes; isopropylthioxanthone;1-hydroxy-cyclohexylphenylketone; benzophenone;2,4,6-trimethylbenzophenone; 4-methylbenzophenone;diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide;2,4,6-trimethylbenzoylphenylphosphinic acid ethyl ester;oligo(2-hydroxy-2-methy-1-(4-(1-methylvinyl)phenyl)propanone);2-hydroxy-2-methyl-1-phenyl-1-propanone; benzyl-dimethylketal; andmixtures thereof. Amine synergists may also be employed, which aredescribed as co-initiators that donate a hydrogen atom to aphotoinitiator and thereby form a radical species that initiatespolymerization (amine synergists can also consume oxygen dissolved inthe ink—as oxygen inhibits free-radical polymerization its consumptionincreases the speed of polymerization), for example such asethyl-4-dimethylaminobenzoate and 2-ethylhexyl-4-dimethylaminobenzoate.This list is not exhaustive, and any known photoinitiator that initiatesthe free-radical reaction upon exposure to a desired wavelength ofradiation such as UV light can be used without limitation.

The photoinitiator may absorb radiation of about 200 to about 420 nmwavelengths in order to initiate cure, although use of initiators thatabsorb at longer wavelengths, such as the titanocenes that may absorb upto 560 nm, can also be used without restriction. The total amount ofinitiator included in the solid build ink may be from, for example,about 0.5 to about 15% by weight, such as from about 1 to about 10% byweight, of the ink composition. In embodiments, the curing speed of eachbuild ink is not only dependent on the selected photoinitiator for eachbuild ink but also on the ratio of curable and non-curable wax in theink.

In specific embodiments, the curable monomers may be present in thesolid build ink in an amount of from about 50 to about 95 percent, orfrom about 60 to about 90 percent by weight of the total weight of thecurable solid ink. The curable wax may be present in the solid build inkin an amount of from about 0.1 to about 30 percent of the total weightof the curable solid ink. The optional gellant may be present in thecurable solid ink in an amount of from about 1 to about 30 percent, orfrom about 5 to about 10 percent by weight of the total weight of thecurable solid ink. In a specific embodiment, the gellant is present inthe curable solid ink in an amount of about 7 percent by weight of thetotal weight of the curable solid ink. The colorant may be present inthe curable solid ink in an amount of from about 0.1 to about 10percent, or from about 1 to about 5 percent by weight of the totalweight of the curable solid ink. The photoinitiator may be present inthe curable solid ink in an amount of from about 0.5 to about 15percent, or from about 1 to about 10 percent by weight of the totalweight of the curable solid ink.

In embodiments, each solid build ink has a different initial hardnessfor each of the plurality of colors.

In embodiments, the plurality of colors comprises cyan, magenta, yellow,and black. In embodiments, when the color is cyan or black, the weightratio of the non-curable wax to curable wax is in a range from about 2:1to about 5:1, or from about 3:1 to about 4.5:1. In embodiments, when thecolor is yellow or magenta, the weight ratio of the non-curable wax tocurable wax is in a range from about 0.5:1 to about 4:1, or from about1:1 to about 3:1.

The amount and type of photoinitiators in each of the colored waxes mayalso be adjusted to achieve a comparable final hardness. In embodiments,the total amount of the mixture of photoinitiators is between about 4 toabout 15 weight percent, with the yellow ink containing from about 4 toabout 10 weight percent and the cyan, magenta and black ink containingfrom about 7 to about 15 weight percent.

In embodiments, a thickness of a layer before curing is a maximum in arange from about 10 microns to about 5 mm. In embodiments, each of buildink has an initial hardness in a range from about 5 to about 60 units,or about 10 to about 50, or about 20 to about 50 units. In embodiments,each build ink has an initial slope representing the initial curing ratein a range from about 25 to about 300 units, or about 100 to about 300units, or about 150 to 300 units.

In embodiments, there are provided methods of color 3D printingcomprising providing a solid build ink for each of a plurality ofcolors, each solid build ink comprising a solid acrylate in an amountfrom about 40 to about 70 percent by weight, a non-curable wax in anamount from about 10 to about 45 percent, a curable wax in an amountfrom about 1 to about 15 percent; a photoinitiator; and a colorant,wherein each solid build ink has an initial curing speed adjusted by aratio of the non-curable wax to curable wax such that the curing speedand final hardness of each solid build ink is approximately the same foreach of the plurality of colors, providing a support material comprisingthe non-curable wax used in each build ink, the support materialproviding a scaffold for deposition of each build ink, depositing one ormore solid build inks in a plurality of layers to form athree-dimensional article on a substrate, curing each of the pluralityof layers, and supporting one or more of the plurality of layers withthe support material.

In embodiments, a thickness of one of the plurality of layers beforecuring is a maximum in a range from about 10 microns to about 5 mm. Inembodiments, methods may further comprise removing the support materialafter completing the three-dimensional article. In embodiments, theremoving step comprises washing, melting or physically removing thesupport material.

In embodiments, methods further comprise blending two or more build inksto form a new color prior to depositing a layer using the blended buildinks. Whether employing single inks or blends/mixtures of inks,embodiments herein encompass inks having substantially the same initialcure rate and final hardness. As used herein, “substantially the same”in connection with initial cure rate and/or final hardness means withinabout 10% of each other, or within about 5% of each other, or withinabout 2% of each other, or within about 1% of each other.

In embodiments, the depositing step employs an inkjet printer. Inembodiments, the curing step comprises UV irradiation.

In embodiments, there are provided three-dimensional articles made bythe methods disclosed herein. In embodiments, a three dimensionallyprinted article described herein comprises a plurality of layers of thesolid build ink, wherein the layers of the solid build ink are depositedaccording to data in a computer readable format. Moreover, one or moreof the deposited layers of solid build ink may be supported by thesupport material described herein. The support material may be removedto complete production of the three-dimensionally printed article orobject.

In another aspect, methods of printing a three-dimensional article orobject are described herein. In embodiments, a method of printing athree-dimensional article comprises selectively depositing layers ofsolid build inks to form the three-dimensional article on a substrate,the solid build inks being available in a variety of colors, andoptionally supporting one or more of the solid build ink layers with thesupport material, the support material comprising a non-curable waxcomponent.

In embodiments, a method of printing a three-dimensional articlecomprises selectively depositing layers of solid build inks, availablein a variety of colors, to form the three-dimensional article on asubstrate, and supporting one or more of the solid build ink layers witha support material, the support material comprising a non-curable waxcomponent and optionally a viscosity modifying component.

In some embodiments, a method of printing a three-dimensional articlefurther comprises curing the solid build ink. This may be done at anystage, including at each individual build ink layer or any combinationof layers, including one cure step of the fully formed three-dimensionalobject. In embodiments, a method of printing a three-dimensional articlefurther comprises subjecting the build ink to electromagnetic radiationof sufficient wavelength and intensity to cure the build material. Inembodiments for printing a three-dimensional article, a layer ofdeposited solid build ink may be cured prior to the deposition ofanother or adjacent layer of build material.

In embodiments, a pre-selected amount of solid build ink may be heatedto the appropriate temperature and jetted through a print head or aplurality of print heads of a suitable inkjet printer to form a layeronto a support platform in a build chamber. Each layer of build ink maybe deposited according to the preselected CAD parameters. A suitableprint head to deposit the build material may include a piezoelectricZ850 print head available from Xerox Corporation, OR. Additionalsuitable print heads for the deposition of build and support materialsdescribed herein are commercially available from a variety of ink jetprinting apparatus manufacturers. For example, the Taipan print headavailable from Xerox or Ricoh print heads may also be used.

In embodiments, the temperature of the build environment can becontrolled so that the jetted droplets of solid build ink solidify oncontact with the receiving surface, in other embodiments, the jetteddroplets of build material do not solidify on contact with the receivingsurface, remaining in a semi-fluid state. In some embodiments, aftereach layer is deposited, the deposited material may be optionallyplanarized and cured with electromagnetic (e.g., UV) radiation prior tothe deposition of the next layer. Optionally, several layers can bedeposited before optional planarization and curing, or multiple layerscan be deposited and cured followed by one or more layers beingdeposited and then optionally planarized without curing. Planarizationmay be used to correct the thickness of one or more layers prior tocuring the solid build ink by evening the dispensed material to removeexcess material and create a uniformly smooth exposed or flat up-facingsurface on the support platform of the printer. In embodiments,planarization may be accomplished with a wiper device, such as a roller,which may be counter-rotating in one or more printing directions but notcounter-rotating in one or more other printing directions. Inembodiments, the wiper device comprises a roller and a wiper thatremoves excess material from the roller. In embodiments, the wiperdevice may be heated. The process is continued until a useful finishedthree-dimensional design is prepared. It should be noted that theconsistency of the jetted solid build ink of the prior to curing may besufficient to retain its shape and not be subject to excessive viscousdrag from the planarizer. In embodiments, the consistency and accuracyof the jetted solid build ink may be sufficient to obviate the need forplanarization.

In embodiments, the support material can be deposited in a mannerconsistent with that described herein for the solid build ink. Thesupport material, for example, can be deposited according to thepreselected CAD parameters such that the support material is adjacent orcontinuous with one or more layers of the build material. Jetteddroplets of the support material may solidify or freeze on contact withthe receiving surface. In some embodiments, the deposited supportmaterial is also optionally subjected to planarization.

Layered deposition of the solid build ink and support material can berepeated until the three-dimensional article has been formed. In someembodiments, a method of printing a three-dimensional article furthercomprises removing the support material from the build material. Assupport materials described herein may be water dispersible and/or atleast partially water soluble, removing the support material from thebuild material, in some embodiments, comprises dispersing the supportmaterial in water. Dispersing the support material in water, in someembodiments, comprises contacting the support material with flowingwater. In some embodiments, dispersing the support material in watercomprises at least partially immersing the three-dimensionally printedarticle in a water bath. In some embodiments, the water bath is stirredduring immersion of the three-dimensionally printed article. In otherembodiments, solvents other than water may be used to wash away thesupport material, such as acetone, methanol, ethanol, 1-propanol,2-propanol, 2-butanol, methyl ethyl ketone, methyl isobutyl ketone, andmixture thereof.

In some embodiments, one or more surfactants or detergents can be addedto water used to remove the support material from the build material.Additionally, in some embodiments, the support material can be subjectedto mechanical agitation. In some embodiments, mechanical agitation ofthe support material is administered by contacting the support materialwith flowing or jetted water. In some embodiments, the support materialcan be subjected to ultrasonic agitation to remove the support materialfrom the build material, in some embodiments, the support material canbe subjected to a combination of mechanical and ultrasonic agitation toremove the support material from the cured build ink.

In embodiments, there are provided sets of solid build inks for use incolor three-dimensional printing, each of the set of solid build inkscomprising a solid acrylate in an amount from about 40 to about 50percent by weight, a non-curable wax in an amount from about 30 to about40 percent, a curable wax in an amount from about 5 to about 10 percent,a photoinitiator, and a colorant, wherein each solid build ink in theset has a different colorant and has a curing speed adjusted by a ratioof the non-curable wax to curable wax such that the curing speed andfinal hardness of each solid build ink is approximately the sameindependent of the colorant in a given solid build ink.

Those skilled in the art will readily be able to apply the teachings andguidance provided herein to generate new ink designs with a set ofdesired properties. Thus, in some embodiments, there are providedmethods of designing a target ink having a desired initial cure rate anddesired final hardness comprising selecting at least one ink from aplurality of established ink designs (such as the established designs inFIG. 3), the at least one ink having an initial cure rate and finalhardness proximal to the desired cure rate and final hardness andpredicting a modification to at least a ratio of a curable wax tonon-curable wax in the at least one ink to provide the target ink. Otherpotential modifications may be dependent on the selection of aparticular colorant and/or photoinitiator.

The following Examples are being submitted to illustrate embodiments ofthe present disclosure. These Examples are intended to be illustrativeonly and are not intended to limit the scope of the present disclosure.Also, parts and percentages are by weight unless otherwise indicated. Asused herein, “room temperature” refers to a temperature of from about20° C. to about 25° C.

EXAMPLES Example 1

This Example describes for formation of exemplary solid build inks andcharacterization of some of their physical properties.

Dyed Ink formulations were prepared as follows: Into a 30 mL amber glassbottle, was added 2.019 g CD406, 1.007 g SR368, 2.843 g CD587, allavailable from Sartomer Company Inc. 0.825 g Unilin 350 Acrylate, anacrylate curable monofunctional acrylate wax C22, C23, C24 mixture ofmelting point between 50 and 60° C., 2.528 g Licowax KFO, an ester waxavailable from Clariant, 0.155 g Irgacure 819, 0.224 g Irgacure 184, and0.100 g Irgacure 907, all available from Ciba Specialty Chemicals. Tothis mixture was added a stir bar and the mixture was placed in aVariomag reaction block. The ink mixture was heated and stirred at 90°C., and 300 RPM respectively for at least 20 minutes or until themixture appeared homogeneous. The temperature was increased to 100° C.for five minutes before 0.300 g Blue Olefin Dye was added. The mixturewas brought back down to 90° C. and left to stir for 1.5 hours, at whichpoint the mixture appeared homogeneous.

Pigmented ink formulations were prepared as follows: Into a 30 mL amberglass bottle, was added 2.019 g CD406, 1.007 g SR368, 2.843 g CD587,0.825 g Unilin 350 Acrylate, 2.528 g Licowax KFO, 0.155 g Irgacure 819,0.224 g Irgacure 184, and 0.100g Irgacure 907. To this mixture was addeda stir bar and the mixture was placed in a Variomag reaction block. Theink mixture was heated and stirred at about 90° C., and 300 RPMrespectively for at least 20 minutes or until mixture appearshomogeneous. The temperature was increased to 100° C. for about fiveminutes after which time 0.300 g Microlith Magenta Pigment was added.The mixture was brought back down to 90° C. and left to stir overnight(16 hours), at which point the mixture appeared homogeneous.

Ink formulations were prepared as follows: Into a 30 mL amber glassbottle was added 2.019 g CD406, 1.007 g SR368, 2.843 g CD587, 0.825 gUnilin 350 Acrylate, 2.528 g Licowax KFO, 0.155 g Irgacure 819, 0.224 gIrgacure 184, and 0.100 g Irgacure 907. To this mixture was added a stirbar and the mixture was placed in a Variomag reaction block. The inkmixture was heated and stirred at 90° C., and 300 RPM respectively forat least 20 minutes or until the mixture appeared homogeneous. Thetemperature was increased to 100° C. for about five minutes and left tostir for ten minutes.

Other examples of curable solid build inks that may fall within theparameters disclosed herein are described in U.S. Patent ApplicationNos. 2012/0287212, 2012/0287199, and 2012/0274699, each of which isincorporated herein by reference in their entirety.

Specific examples of curable solid build inks suitable forthree-dimensional printing processes are shown in the Table 1 below.Formulations O1 to O3 were chosen to cover a range of curing propertieswhile still being homogeneous as well as having the correct viscosity atjetting temperature.

TABLE 1 Component O1 O2 O3 L1 Monomer CD406 31.105 28.861 20.600 20.394SR368 0 2.244 10.250 10.172 CD587 17.581 17.581 29.010 28.724 CurableWax Unilin 350 8.330 8.330 8.330 8.330 acrylate Non-curable wax LicowaxKFO 36.142 0 0 25.539 Igepal A 0 36.142 24.970 0 Photoinitiator Irgacure819 1.568 1.568 1.570 1.570 Irgacure 184 2.264 2.264 2.260 2.258Irgacure 907 1.009 1.009 1.010 1.013 Colorant Blue Olefin Dye 2.00 2.002.00 2.00 TOTAL 100 100 100 100

Rheological profiles for inks of invention are shown in FIG. 1. The inksare Newtonian in temperature range from about 80° C. to about 90° C.Curing profiles of analogous formulations without colorants was alsoobtained as indicated in FIG. 2 and in Table 2 below. Note, forsimplicity the data was generated without colorant to provide convenientcomparison of formulations without regard to the impact of the colorant.One skilled in the art will recognize, however, that the one can includea colorant and determine an optimum photoinitiator package for each ofthe color and compare them at this optimum.

The data in Table 2 was extracted from fitting data of FIG. 2 using therelationship:

y=m ₁ +m ₂·(1−exp(−m ₃ ·x))

Initial Hardness=m₁

Initial Slope=m ₂ ·m ₃

Final Hardness=m ₁ +m ₂

TABLE 2 Predicted Properties (Analogous formulations with no colorant)Initial Hardness 50.4 33.5 17.8 Final Hardness 82.3 82.9 81.4 InitialSlope 46 214 280

Numerous curable solid build inks were formulated to define the designspace for printing. While fast curing rates are useful for conventionalprinting processes where initial hardness is below about 20, the solidbuild inks disclosed herein have an initial hardness generally aboveabout 30 with initial slope above about 25. In embodiments, the initialhardness may be lower but in such cases, the materials should have avery high curing rate, such as an initial slope of more than about 200.

FIG. 3 shows a plot of initial slope versus initial hardness for avariety of solid build inks prepared in accordance with embodimentsherein. The upper right quadrant represents a beneficial operatinglocation for materials, that is, fastest initial curing rate (initialslope) or highest initial hardness. For 3D object printing, a lowerinitial hardness is acceptable provided it is high enough to preventflow at ambient temperature within timeframe of building the object. Thefollowing tabulated series of inks exemplify 3D formulations inaccordance with embodiments herein and were used to generate the datashown in FIG. 3.

TABLE 3 Ink # 1 2 3 4 5 6 7 8 9 10 CD406 2.00 2.00 4.74 3.34 2.74 6.006.00 2.00 2.00 3.57 SR368 1.44 2.10 0.70 2.10 0.70 1.44 0.70 2.10 2.101.25 CD587 4.00 3.34 0.00 0.00 4.00 0.00 0.00 1.34 1.34 1.57 Unilin 3500.00 0.00 0.00 2.00 0.00 0.00 0.74 2.00 0.00 0.53 acrylate Licowax KFO2.00 2.00 4.00 2.00 2.00 2.00 2.00 2.00 4.00 2.53 ITX 0.05 0.05 0.050.05 0.05 0.05 0.05 0.05 0.05 0.05 Irgacure 907 0.51 0.51 0.51 0.51 0.510.51 0.51 0.51 0.51 0.51 Total 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.010.0 10.0 Ink # 11 12 13 14 15 16 17 18 19 20 CD406 2.00 3.57 2.00 2.002.00 6.00 5.34 4.74 3.34 6.00 SR368 0.70 1.25 0.70 0.70 0.70 0.70 2.100.70 2.10 0.70 CD587 2.74 1.57 4.00 2.74 4.00 0.74 0.00 0.00 0.00 0.00Unilin 350 2.00 0.53 0.00 0.00 0.74 0.00 0.00 2.00 0.00 0.00 acrylateLicowax KFO 2.000 2.527 2.740 4.000 2.000 2.000 2.000 2.000 4.000 2.740ITX 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Irgacure 907 0.510.51 0.51 0.51 0.51 0.51 0.51 0.51 0.51 0.51 Total 10.0 10.0 10.0 10.010.0 10.0 10.0 10.0 10.0 10.0

TABLE 4 Ink # 21 22 23 24 25 26 27 28 Monomer CD406 2.000 2.000 2.0002.010 2.901 2.000 2.000 2.010 SR368 1.025 1.025 1.025 1.030 1.600 1.0251.025 1.030 CD587 3.037 3.037 3.037 3.052 2.563 3.037 3.037 3.052Curable Wax Unilin 350 0.806 0.806 0.806 0.810 0.374 0.806 0.806 0.810acrylate Oligomer CN2255 0.000 0.000 0.000 0.000 0.000 0.077 0.000 0.000CN2256 0.000 0.000 0.000 0.000 0.000 0.000 0.077 0.000 Non-Curable WaxLicoWax KFO 2.570 2.570 2.570 2.583 2.000 2.493 2.493 2.583Photoinitiator Darocur ITX 0.050 0.050 0.050 0.050 0.050 0.050 0.0500.000 Irgacure 907 0.510 0.510 0.510 0.513 0.510 0.510 0.510 0.513 Total10.00 10.00 10.00 10.05 10.00 10.00 10.00 10.00

TABLE 5 Ink # 29 30 31 32 33 34 35 36 37 38 Monomer CD406 2.08 2.08 2.082.08 2.08 2.08 2.08 2.08 2.08 2.08 SR368 1.04 1.04 1.04 1.04 1.04 1.041.04 1.04 1.04 1.04 CD587 2.93 2.93 2.93 2.93 2.93 2.93 2.93 2.93 2.932.93 Curable Wax Unlin 350 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.850.85 acrylate Non-Curable Wax Licowax KFO 1.60 1.70 1.60 1.80 1.94 2.702.20 1.60 2.30 2.10 Photoinitiator Irgacure 819 0.30 0.30 0.10 0.10 0.190.10 0.10 0.30 0.10 0.30 Irgacure 184 0.10 0.50 0.30 0.50 0.31 0.10 0.100.50 0.10 0.10 Irgacure 379 0.50 0.50 0.50 0.10 0.31 0.10 0.10 0.50 0.500.50 Irgacure 907 0.60 0.10 0.60 0.60 0.34 0.10 0.60 0.20 0.10 0.10Total 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Ink # 11 12 1314 15 16 17 18 19 Monomer CD406 2.08 2.08 2.08 2.08 2.08 2.08 2.08 2.082.08 SR368 1.04 1.04 1.04 1.04 1.04 1.04 1.04 1.04 1.04 CD587 2.93 2.932.93 2.93 2.93 2.93 2.93 2.93 2.93 Curable Wax Unlin 350 0.85 0.85 0.850.85 0.85 0.85 0.85 0.85 0.85 acrylate Non-Curable Wax Licowax KFO 1.601.80 2.00 2.10 1.60 2.30 1.90 2.50 1.60 Photoinitiator Irgacure 819 0.100.10 0.30 0.30 0.10 0.10 0.10 0.30 0.30 Irgacure 184 0.50 0.10 0.10 0.500.50 0.50 0.50 0.10 0.50 Irgacure 379 0.30 0.50 0.10 0.10 0.50 0.10 0.500.10 0.10 Irgacure 907 0.60 0.60 0.60 0.10 0.40 0.10 0.10 0.10 0.60Total 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0

TABLE 6 Ink # 39 40 41 42 43 44 45 46 47 Monomer CD406 2.081 2.081 2.0812.081 2.081 2.081 2.081 2.081 2.010 SR368 1.038 1.038 1.038 1.038 1.0381.038 1.038 1.038 1.030 CD587 2.931 2.931 2.931 2.931 2.931 2.931 2.9312.931 3.052 Curable Wax Unilin 350 0.850 0.850 0.850 0.850 0.850 0.8500.850 0.850 0.810 acrylate Licowax KFO 2.522 2.606 2.606 2.655 2.7172.522 0.000 2.217 2.326 Photoinitiator Irgacure 819 0.155 0.160 0.1600.000 0.167 0.000 0.155 0.100 0.000 Irgacure 184 0.223 0.230 0.230 0.2350.000 0.581 0.223 0.353 0.000 Irgacure 907 0.100 0.103 0.000 0.105 0.1080.000 0.100 0.330 0.513 Total 10.00 10.00 10.00 10.00 10.00 10.00 10.0010.00 10.00

TABLE 7 Ink # 48 49 50 51 52 53 Monomer CD406 2.945 2.945 2.945 2.4423.234 2.945 SR368 0.229 0.229 0.229 0.319 0.251 0.229 CD587 1.794 1.7941.794 2.501 1.970 1.794 Curable Wax Unilin 350 0.850 0.850 0.850 1.1850.000 0.850 acrylate Non-Curable Wax Licowax KFO 3.688 0.000 0.000 0.0004.050 2.889 Igepal A 0.000 3.688 0.000 3.058 0.000 0.800 Igepal D 0.0000.000 3.688 0.000 0.000 0.000 Photoinitiator Irgacure 819 0.160 0.1600.160 0.160 0.160 0.160 Irgacure184 0.231 0.231 0.231 0.231 0.231 0.231Irgacure 907 0.103 0.103 0.103 0.103 0.103 0.103 Total 10.00 10.00 10.0010.00 10.00 10.00

TABLE 8 Ink # 54 55 56 57 Monomer CD406 2.234 2.234 2.234 3.174 SR3680.174 0.174 0.174 0.000 CD587 1.361 1.361 1.361 1.794 Curable Wax Unilin350 acrylate 0.850 0.850 0.850 0.850 Non-Curable Wax Licowax KFO 0.0000.000 0.000 3.688 Igepal A 4.888 0.000 4.088 0.000 Igepal D 0.000 4.8880.000 0.000 Amide Gellant 0.000 0.000 0.800 0.000 PhotoinitiatorIrgacure 819 0.160 0.160 0.160 0.160 Irgacure 184 0.231 0.231 0.2310.231 Irgacure 907 0.103 0.103 0.103 0.103 Total 10.00 10.00 10.00 10.00

Each of the inks included in Table 3 to Table 8 were evaluated using thesame method that was used for the inks of Table 1, thus generating“initial slope” (initial curing rate) and “initial hardness” data foreach of them. The data was then plotted (FIG. 3) to help define theformulation design latitude/space. This is visually represented by thecurved solid line encompassing the data points in FIG. 3. Based on theresults one can predict inks with properties intermediate to those shownin Table 3 and such inks can be formulated by changing the ratio of theexisting ink components. Inks with intermediate properties can also begenerated by combining compositions whose data points are in closeproximity to one another (see FIG. 3). Thus, it becomes possible toadjust the formulations of an ink set so that all colors will haveapproximately the same initial hardness and curing rate. Optionally,this approach can be used to formulate building materials that havedifferent starting initial properties and different cured properties,thus generating parts that have controlled curing profiles. This may beuseful, for example, when the surface of a part is required to bedifferent from the bulk of the part or when individual sections of thepart of a printed object need to have different initial curingproperties to allow post-processing.

What is claimed is:
 1. A set of solid build inks for use in colorthree-dimensional printing, each of the set of solid build inkscomprising: a solid acrylate in an amount from about 40 to about 70percent by weight; a non-curable wax in an amount from about 10 to about45 percent by weight; a curable wax in an amount from about 1 to about15 percent by weight; a photoinitiator; and a colorant; wherein eachsolid build ink in the set has a different colorant and has a curingspeed adjusted by a weight ratio of the non-curable wax to curable waxsuch that the curing speed and final hardness of each solid build ink issubstantially the same independent of the colorant in a given solidbuild ink.
 2. The set of solid build inks of claim 1, wherein when thecolor is cyan or black, the weight ratio of the non-curable wax tocurable wax is in a range from about 2:1 to about 5:1, and when thecolor is yellow or magenta, the weight ratio of the non-curable wax tocurable wax is in a range from about 0.5:1 to about 4:1.
 3. A set ofsolid build inks for use in color three-dimensional printing, each ofthe set of solid build inks comprising: a solid acrylate in an amountfrom about 40 to about 70 percent by weight; a non-curable wax in anamount from about 10 to about 45 percent by weight; a curable wax in anamount from about 1 to about 15 percent by weight; a photoinitiator; anda colorant; wherein each solid build ink in the set has a differentcolorant and has a curing speed adjusted by a weight ratio of thenon-curable wax to curable wax such that the curing speed and finalhardness of some of the solid build inks is substantially different fromone another.